CN102861357A - Bionic dental implant and preparation method thereof - Google Patents
Bionic dental implant and preparation method thereof Download PDFInfo
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- CN102861357A CN102861357A CN2012103847311A CN201210384731A CN102861357A CN 102861357 A CN102861357 A CN 102861357A CN 2012103847311 A CN2012103847311 A CN 2012103847311A CN 201210384731 A CN201210384731 A CN 201210384731A CN 102861357 A CN102861357 A CN 102861357A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
Disclosed is a bionic dental implant. The bionic dental implant is composed of a titanium substrate, a polyurethane permeating porous titanium dioxide layer and a polyurethane layer which serves as a bionic periodontal membrane, and the polyurethane permeating porous titanium dioxide layer is located between the titanium substrate and the polyurethane layer and respectively and closely integrated with the titanium substrate and the polyurethane layer. A preparation method includes that (1) the titanium substrate is subjected to acid treatment, and then micron grade titanium dioxide powders are deposited layer by layer on the surface of the titanium substrate which is subjected to the acid treatment through an electron beam melting technology to form a porous titanium dioxide layer; (2) isophorone diisocyanate and polyethylene glycol or polyoxytetramethylene glycol or polycaprolactone are used as raw materials to prepare a polyurethane prepolymer; (3) the polyurethane prepolymer is coated on the porous titanium dioxide layer, and then the polyurethane layer is formed under the vacuum condition; and (4) a composite with the polyurethane layer on the surface is soaked in a chain extender solution, a catalyst is added in the solution to react, and after the reaction is finished, the composite is taken out of the chain extender solution and naturally dried by airing in the air.
Description
Technical field
The invention belongs to the Dental Implant field, particularly a kind of surface coverage has pericemental pure-titanium tooth implantation of low modulus class and preparation method thereof.
Background technology
Since Branemark proposed the bone Integration Theory, Dental Implant successfully was used for repairing the permanent teeth disappearance, rebuilds masticatory function.The tooth implantation systems such as the internationally renowned brand tooth implantation system (comprising Britain Branemark, Switzerland ITI, German IMZ, U.S. 3i) of commonly using both at home and abroad at present and domestic Leiden BLB all adopt commercial pure titanium as tooth implant, but find in the clinical practice, even import titanium implant, still have becoming flexible in various degree in the use procedure, come off, the problems such as fracture and surrounding bone tissue inflammation, cause and plant unsuccessfully.The Long-term clinical follow-up study finds that the topmost reason of Dental Implant failure is that material/organizational interface's mechanical property is incompatible.As everyone knows, the anatomical structure difference of people's tooth and Dental Implant most critical is pericemental having or not.Natural teeth is suspended in the jawbone by periodontal membrane, and when tooth was stressed, jawbone is evenly transmitted and be dispersed to external force by periodontal membrane, thereby causes periodontal tissue to the physiologic response of External Force Acting; And between synosteosis tooth implant and the jawbone for being rigidly connected, the two directly contacts, lack periodontal membrane, when tooth implant elastic modelling quantity and jawbone elastic modelling quantity are inconsistent, it is directly to reach its surrounding bone tissue by tooth implant that implant denture is subject to the impact energy that shock loading produces, easily cause tooth implant surrounding bone structural stress to be concentrated, cause on every side bone absorption or atrophy, thereby make the canine implant failure.The elastic modelling quantity of the used commercial pure titanium of present clinical tooth implant is 110GPa, far above the elastic modelling quantity 10 ~ 18GPa of people's mandibular bone cortical bone and the elastic modelling quantity 1.5 ~ 2.5GPa of spongy bone.From medical science and mechanics angle, the elastic modelling quantity of implantation body's material is less, and more near the elastic modelling quantity of bone, both are less in response to the different relative displacement that causes of variation when meeting with stresses, can reduce the loosening tendency in interface, bone resorption and the degeneration of avoiding stress shielding to cause.But along with the elastic modelling quantity of metal material reduces, its intensity and rigidity be corresponding reduction also, then be difficult to carry the ambient stress of oral cavity complexity, if the biomechanical compatibility problem after merely solving it and implant by the elastic modelling quantity that reduces tooth implant then has the suspicion of attending trifles and neglect essentials.Long-term follow-up results of dural research all shows, the mechanical performance of pure titanium implant excellence can satisfy the carrying environmental requirement of oral cavity complexity well, if can effectively solve its mechanical compatibility problem, its service life in vivo ultranatural tooth far away then significantly improves the success rate at a specified future date of implant denture.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of bionic tooth implant and preparation method thereof is provided, to solve the biomechanical compatibility problem of tooth implant.
The present invention is from bionics principle, introduce bionical periodontal membrane concept, in pure titanium surface preparation low-modulus polyurethane coating, to imitate natural pericemental biomechanical function, give Dental Implant rational physiological mobility, and gmatjpdumamics played conduction and cushioning effect, alveolar bone interface upper stress is evenly distributed, thereby solves the biomechanical compatibility problem of pure titanium implant.
Bionic tooth implant of the present invention, the poriferous titanium dioxide layer of polyurethane is arranged and consist of as bionical pericemental layer of polyurethane by titanio body, infiltration, described infiltration has the poriferous titanium dioxide layer of polyurethane between titanio body and layer of polyurethane, is closely as one with titanio body, layer of polyurethane respectively.
Because natural teeth is suspended in the jawbone by the periodontal membrane of thick about 0.2mm, when tooth was stressed, jawbone is evenly transmitted and be dispersed to external force by periodontal membrane, thereby cause periodontal tissue to the physiologic response of External Force Acting.Thereby the THICKNESS CONTROL of bionic tooth implant of the present invention is at 0.15mm～0.25mm, to adapt to all ages and classes patient's plantation demand.
The preparation method of bionic tooth implant of the present invention, processing step is as follows:
1. the titanio body is carried out acid treatment, then use electron beam fusion technology (EBM) at the acid-treated titanio of process surface layer by layer deposition micron order titania powder, form the poriferous titanium dioxide layer that runs through and be rich in the Ti-OH active group between the coexistence of micron and nanoscale hole and hole, the amount of described titania powder is limited as the poriferous titanium dioxide layer of 0.15mm ~ 0.3mm can form thickness;
2. with isophorone diisocyanate (IPDI), Polyethylene Glycol (PEG) or PTMG (PTMG) or polycaprolactone (PCL) prepare base polyurethane prepolymer for use as for raw material, the mol ratio of isophorone diisocyanate and Polyethylene Glycol or PTMG or polycaprolactone is 1.2:1～1:1, with the isophorone diisocyanate that measures, thermometer is equipped with in Polyethylene Glycol or PTMG or polycaprolactone adding, in the reaction vessel of reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 70 ℃ ~ 80 ℃ lower reaction 2 h ~ 3 h namely obtain having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into hermetic container, evacuation, the negative pressure 0.5h of maintenance 0.01Mpa～0.06MPa ~ 1h, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and forming the liquid polyurethane layer of one deck drawout on the surface of poriferous titanium dioxide layer, the amount of described base polyurethane prepolymer for use as is limited as the layer of polyurethane of 0.15mm～0.25mm can form thickness;
4. the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the expanding chain pharmaceutical solution that chain extender concentration is 0.3g/ml ~ 0.8g/ml, and the inferior stannum of adding octoate catalyst, then under normal pressure, be heated to 50 ℃～55 ℃ insulation 2 h ~ 3h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, namely obtain bionic tooth implant, the amount of described expanding chain pharmaceutical solution has the compound physical ability of layer of polyurethane to flood fully with the surface to be limited, and the inferior stannum of described octoate catalyst is 0. 2% ~ 0. 5% of expanding chain pharmaceutical solution volume.
In the said method, chain extender is triethanolamine or trimethylolpropane, and the chain extender solvent is acetone or DMF.
In the said method, the preferred 50 μ m of the particle diameter of titania powder ~ 100 μ m.
Described electron beam melting technology is that the heat that utilizes high-power electron beam to produce forms localized hyperthermia, make the local thawing of titania powder, and by continuous sweep the partial melting position is merged mutually, connect into wire or planar metal level, by successively melting, mutually run through and be rich in the poriferous titanium dioxide layer of Ti-OH active group between cumulative formation micron and the coexistence of nanoscale hole and hole.But the technique reference papers of electron beam melting technology " electron beam melting make fast Ti-6Al-4V mechanical property (lock red ripple etc., Aerospace manufacturing technology, 2009.12 (06): 18-22) ".
The present invention has following beneficial effect:
1, because the outer surface of bionic tooth implant of the present invention is coated with layer of polyurethane, and polyurethane elastomer shows and is very similar to natural pericemental low elastic modulus and non-linear viscosity property, and have excellent erosion resistant, the characteristic such as pliable and tough, thereby with respect to existing tooth implant, biomechanical compatibility is better, and the plantation success rate improves.
2, because the pure titanio body of bionic tooth implant of the present invention has the poriferous titanium dioxide layer of polyurethane to be combined by infiltration between layer of polyurethane, thereby in conjunction with tight.
3, in the preparation method of bionic tooth implant of the present invention, prepare the liquid polyurethane performed polymer take isophorone diisocyanate, Polyethylene Glycol, PTMG or polycaprolactone as raw material, thereby formed layer of polyurethane avirulence, harmless to human body.
4, because the preparation method of bionic tooth implant of the present invention adopts the electron beam melting technology to form the poriferous titanium dioxide layer, thereby not only can effectively get rid of extraneous chemical element impurity to pollution and the harm of material production, and so that chain extending reaction can carry out more fully, monomer utilization ratio improves, and layer of polyurethane is combined firmly with matrix.
5, because the preparation method of bionic tooth implant of the present invention adopts the mode of negative pressure-pumping the liquid polyurethane performed polymer fully to be penetrated in the hole of poriferous titanium dioxide layer, form the reactor of many micro/nano levels at pure titanio body, thereby reaction efficiency and speed have been improved, and adopt this mode chain extension, can control the thickness of formed polyurethane coating by the speed and the time that change chain extending reaction, make it reach the requirement of tooth implant.
6, the preparation method of bionic tooth implant of the present invention is used conventional equipment, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 be bionic tooth implant of the present invention cross-sectional view, among the figure, 1-titanio body, 2-infiltration has poriferous titanium dioxide layer, the 3-layer of polyurethane of polyurethane.
The specific embodiment
Below by embodiment bionic tooth implant of the present invention and preparation method thereof is described in further detail.
In the present embodiment, the processing step of preparation bionic tooth implant is as follows:
1. the titanio body is the bone screw of diameter=4.5mm, a length=12mm, the mixed acid of titanio body and function hydrochloric acid and sulphuric acid composition is processed, the mass concentration of hydrochloric acid is 36%, the mass concentration of sulphuric acid is 98%, preparation 20ml mixed acid, in the mixed acid, the volume ratio of hydrochloric acid and sulphuric acid is 1:1, processing method: will put into the beaker that fills described mixed acid through the titanio body of polishing, with described beaker with preservative film sealing and put into 60 ℃ water-bath, take out the titanio body behind the constant temperature 30min, and the titanio body is put into baking oven 50 ℃ of oven dry;
Adopt the electron beam melting technology at the acid-treated pure titanio of process surface layer by layer deposition titania powder, form the poriferous titanium dioxide layer that runs through and be rich in the Ti-OH active group between the coexistence of micron and nanoscale hole and hole, the particle diameter of described titania powder is 50 μ m ~ 100 μ m, described electron gun vacuum is 0.6Mpa, power is 5.0kW, and accelerating potential is 30 ~ 60kV, and scanning speed is 800mm/min, electron beam current is 2.0mA, and the thickness of poriferous titanium dioxide layer is 0.15mm;
2. take isophorone diisocyanate (IPDI), PTMG 2000(PTMG-2000) prepare base polyurethane prepolymer for use as raw material, with 13g isophorone diisocyanate (IPDI) and 50g PTMG 2000(PTMG-2000) add and be equipped with in the there-necked flask of thermometer, reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 70 ℃ of lower reaction 2h, (the mol ratio of IPDI and PTMG-2000=1.2:1) that obtains having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as 1.2g that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into vacuum pump, evacuation, the negative pressure 0.5h that keeps 0.06MPa, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and form the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer;
4. with the chain extender trimethylolpropane (TMP) of 7.0g and the N of 10ml, dinethylformamide (DMF) is mixed with solution and is contained in the beaker of 50ml, the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the above-mentioned expanding chain pharmaceutical solution, and splash into the inferior stannum of 0.05ml octoate catalyst, then described beaker is put into 55 ℃ baking oven insulation 2 h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, can obtain shown in Figure 1 successively by pure titanio body 1, infiltration has the poriferous titanium dioxide layer 2 of polyurethane and the bionic tooth implant that layer of polyurethane 3 consists of, and the thickness of layer of polyurethane is about 0.20mm.
The bionic tooth implant that present embodiment is prepared carries out scratch test, result of the test shows, when producing micro-crack in the layer of polyurethane, all do not produce break-off between the poriferous titanium dioxide layer that permeate between the poriferous titanium dioxide layer and layer of polyurethane that polyurethane is arranged, infiltration has polyurethane and the titanio body, show between them in conjunction with tight.The bionic tooth implant that present embodiment is prepared is immersed in 24h in 37 ℃ of supersaturation calcium phosphate solution, has a certain amount of class HA crystal to grow on the layer of polyurethane surface, shows that the prepared bionic tooth implant biocompatibility of present embodiment is good.
Embodiment 2
In the present embodiment, the processing step of preparation bionic tooth implant is as follows:
1. the titanio body is the bone screw of diameter=4.5mm, a length=12mm, and the acid treatment of titanio body is identical with embodiment 1; Adopt the electron beam melting technology at the acid-treated pure titanium of process surface layer by layer deposition titania powder, form the poriferous titanium dioxide layer, the particle diameter of described titania powder is 50 μ m ~ 100 μ m, described electron gun vacuum is 0.6Mpa, power is 5.0kW, and accelerating potential is 30 ~ 60kV, and scanning speed is 800mm/min, electron beam current is 2.0mA, and the thickness of poriferous titanium dioxide layer is 0.20mm;
2. take isophorone diisocyanate (IPDI), polycaprolactone 2000(PCL-2000) prepare base polyurethane prepolymer for use as raw material, with 10g isophorone diisocyanate (IPDI) and 50g polycaprolactone 2000(PCL-2000) add and be equipped with in the there-necked flask of thermometer, reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 75 ℃ of lower reaction 3h, (the mol ratio of IPDI and PCL-2000=1:1) that obtains having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as 1.0g that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into vacuum pump, evacuation, the negative pressure 1h that keeps 0.06MPa, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and form the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer;
4. with the chain extender trimethylolpropane (TMP) of 6.0g and the N of 10ml, dinethylformamide (DMF) is mixed with solution and is contained in the beaker of 50ml, the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the above-mentioned expanding chain pharmaceutical solution, and splash into the inferior stannum of 0.03ml octoate catalyst, then described beaker is put into 55 ℃ baking oven insulation 3 h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, can obtain shown in Figure 1 successively by pure titanio body 1, infiltration has the poriferous titanium dioxide layer 2 of polyurethane and the bionic tooth implant that layer of polyurethane 3 consists of, and the thickness of layer of polyurethane is about 0.15mm.
The bionic tooth implant that present embodiment is prepared carries out scratch test, result of the test shows, when producing micro-crack in the layer of polyurethane, all do not produce break-off between the poriferous titanium dioxide layer that permeate between the poriferous titanium dioxide layer and layer of polyurethane that polyurethane is arranged, infiltration has polyurethane and the titanio body, show between them in conjunction with tight.The bionic tooth implant that present embodiment is prepared is immersed in 24h in 37 ℃ of supersaturation calcium phosphate solution, has a certain amount of class HA crystal to grow on the layer of polyurethane surface, shows that the prepared bionic tooth implant biocompatibility of present embodiment is good.
In the present embodiment, the processing step of preparation bionic tooth implant is as follows:
1. the titanio body is the bone screw of diameter=4.5mm, a length=12mm, and the acid treatment of titanio body is identical with embodiment 1; Adopt the electron beam melting technology at the acid-treated titanio of process surface layer by layer deposition titania powder, form the poriferous titanium dioxide layer, the particle diameter of described titania powder is 50 μ m ~ 100 μ m, described electron gun vacuum is 0.6Mpa, power is 5.0kW, and accelerating potential is 30 ~ 60kV, and scanning speed is 800mm/min, electron beam current is 2.0mA, and the thickness of poriferous titanium dioxide layer is 0.25mm;
2. take isophorone diisocyanate (IPDI), PTMG 1000(PTMG-1000) prepare base polyurethane prepolymer for use as raw material, with 12g isophorone diisocyanate (IPDI) and 25g PTMG 1000(PTMG-1000) add and be equipped with in the there-necked flask of thermometer, reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 80 ℃ of lower reaction 2.5h, (the mol ratio of IPDI and PTMG-1000=1.1:1) that obtains having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as 1.5g that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into vacuum pump, evacuation, the negative pressure 1h that keeps 0.01MPa, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and form the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer;
4. with the chain extender trimethylolpropane (TMP) of 7.5g and the N of 10ml, dinethylformamide (DMF) is mixed with solution and is contained in the beaker of 50ml, the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the above-mentioned expanding chain pharmaceutical solution, and splash into the inferior stannum of 0.05ml octoate catalyst, then described beaker is put into 55 ℃ baking oven insulation 2.5 h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, can obtain shown in Figure 1 successively by titanio body 1, infiltration has the poriferous titanium dioxide layer 2 of polyurethane and the bionic tooth implant that layer of polyurethane 3 consists of, and the thickness of layer of polyurethane is about 0.25mm.
The bionic tooth implant that present embodiment is prepared carries out scratch test, result of the test shows, when producing micro-crack in the layer of polyurethane, all do not produce break-off between the poriferous titanium dioxide layer that permeate between the poriferous titanium dioxide layer and layer of polyurethane that polyurethane is arranged, infiltration has polyurethane and the titanio body, show between them in conjunction with tight.The bionic tooth implant that present embodiment is prepared is immersed in 24 h in 37 ℃ of supersaturation calcium phosphate solution, has a certain amount of class HA crystal to grow on the layer of polyurethane surface, shows that the prepared bionic tooth implant biocompatibility of present embodiment is good.
Embodiment 4
In the present embodiment, the processing step of preparation bionic tooth implant is as follows:
1. the titanio body is the bone screw of diameter=4.5mm, a length=12mm, and the acid treatment of titanio body is identical with embodiment 1; Adopt the electron beam melting technology at the acid-treated titanio of process surface layer by layer deposition titania powder, form the poriferous titanium dioxide layer, the particle diameter of described titania powder is 50 μ m ~ 100 μ m, described electron gun vacuum is 0.6Mpa, power is 5.0kW, and accelerating potential is 30 ~ 60kV, and scanning speed is 800mm/min, electron beam current is 2.0mA, and the thickness of poriferous titanium dioxide layer is 0.15mm;
2. prepare the liquid polyurethane performed polymer take isophorone diisocyanate (IPDI), cetomacrogol 1000 (PEG-1000) as raw material, 17g isophorone diisocyanate (IPDI) and 25g cetomacrogol 1000 (PEG-1000) adding are equipped with in the there-necked flask of thermometer, reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 70 ℃ of lower reaction 3h, (the mol ratio of IPDI and PEG-1000=1.2:1) that obtains having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as 1.5g that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into vacuum pump, evacuation, the negative pressure 1h that keeps 0.03MPa, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and form the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer;
4. 4.5g chain extender triethanolamine (TEOA) is contained in the beaker of 50ml after with the 10ml acetone diluted, the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the above-mentioned expanding chain pharmaceutical solution, and splash into the inferior stannum of 0.06ml octoate catalyst, then described beaker is put into 50 ℃ baking oven insulation 2.5 h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, can obtain shown in Figure 1 successively by pure titanio body 1, infiltration has the poriferous titanium dioxide layer 2 of polyurethane and the bionic tooth implant of the structure that layer of polyurethane 3 consists of, and the thickness of layer of polyurethane is about 0.25mm.
The bionic tooth implant that present embodiment is prepared carries out scratch test, result of the test shows, when producing micro-crack in the layer of polyurethane, all do not produce break-off between the poriferous titanium dioxide layer that permeate between the poriferous titanium dioxide layer and layer of polyurethane that polyurethane is arranged, infiltration has polyurethane and the titanio body, show between them in conjunction with tight.The bionic tooth implant that present embodiment is prepared is immersed in 24 h in 37 ℃ of supersaturation calcium phosphate solution, has a certain amount of class HA crystal to grow on the layer of polyurethane surface, shows that the prepared bionic tooth implant biocompatibility of present embodiment is good.
Embodiment 5
In the present embodiment, the processing step of preparation bionic tooth implant is as follows:
1. the titanio body is the bone screw of diameter=4.5mm, a length=12mm, and the acid treatment of titanio body is identical with embodiment 1; Adopt the electron beam melting technology at the acid-treated titanio of process surface layer by layer deposition titania powder, form the poriferous titanium dioxide layer, the particle diameter of described titania powder is 50 μ m ~ 100 μ m, described electron gun vacuum is 0.6Mpa, power is 5.0kW, and accelerating potential is 30 ~ 60kV, and scanning speed is 800mm/min, electron beam current is 2.0mA, and the thickness of poriferous titanium dioxide layer is 0.30mm;
2. prepare the liquid polyurethane performed polymer take isophorone diisocyanate (IPDI), Macrogol 2000 (PEG-2000) as raw material, 15g isophorone diisocyanate (IPDI) and 50g Macrogol 2000 (PEG-2000) adding are equipped with in the there-necked flask of thermometer, reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 70 ℃ of lower reaction 2.5h, (the mol ratio of IPDI and PEG-2000=1.1:1) that obtains having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as 1.1g that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into vacuum pump, evacuation, the negative pressure 0.5h that keeps 0.03MPa, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and form the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer;
4. 3.4g chain extender triethanolamine (TEOA) is contained in the beaker of 50ml after with the 10ml acetone diluted, the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the above-mentioned expanding chain pharmaceutical solution, and splash into the inferior stannum of 0.04ml octoate catalyst, then described beaker is put into 50 ℃ baking oven insulation 3 h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, can obtain shown in Figure 1 successively by pure titanio body 1, infiltration has the poriferous titanium dioxide layer 2 of polyurethane and the bionic tooth implant that layer of polyurethane 3 consists of, and the thickness of layer of polyurethane is about 0.17mm.
The bionic tooth implant that present embodiment is prepared carries out scratch test, result of the test shows, when producing micro-crack in the layer of polyurethane, all do not produce break-off between the poriferous titanium dioxide layer that permeate between the poriferous titanium dioxide layer and layer of polyurethane that polyurethane is arranged, infiltration has polyurethane and the titanio body, show between them in conjunction with tight.The bionic tooth implant that present embodiment is prepared is immersed in 24 h in 37 ℃ of supersaturation calcium phosphate solution, has a certain amount of class HA crystal to grow on the layer of polyurethane surface, shows that the prepared bionic tooth implant biocompatibility of present embodiment is good.
Claims (5)
1. bionic tooth implant, it is characterized in that the poriferous titanium dioxide layer (2) of polyurethane is arranged and consisting of as bionical pericemental layer of polyurethane (3) by titanio body (1), infiltration, described infiltration has the poriferous titanium dioxide layer (2) of polyurethane to be positioned between titanio body (1) and the layer of polyurethane (3), is closely as one with titanio body (1), layer of polyurethane (3) respectively.
2. described bionic tooth implant according to claim 1, it is characterized in that permeating the thickness that the poriferous titanium dioxide of polyurethane layer (2) is arranged is 0.15 ~ 0.3mm, the thickness of layer of polyurethane (3) is 0.15mm～0.25mm.
3. the preparation method of a bionic tooth implant is characterized in that processing step is as follows:
1. the titanio body is carried out acid treatment, then use the electron beam fusion technology at the acid-treated titanio of process surface layer by layer deposition micron order titania powder, form the poriferous titanium dioxide layer that runs through and be rich in the Ti-OH active group between the coexistence of micron and nanoscale hole and hole, the amount of described titania powder is limited as the poriferous titanium dioxide layer of 0.15mm ~ 0.3mm can form thickness;
2. with isophorone diisocyanate, Polyethylene Glycol or PTMG or polycaprolactone are that raw material prepares base polyurethane prepolymer for use as, the mol ratio of isophorone diisocyanate and Polyethylene Glycol or PTMG or polycaprolactone is 1.2:1～1:1, with the isophorone diisocyanate that measures, thermometer is equipped with in Polyethylene Glycol or PTMG or polycaprolactone adding, in the reaction vessel of reflux condensing tube and agitator, in nitrogen protection and under stirring in normal pressure, 70 ℃ ~ 80 ℃ lower reaction 2 h ~ 3 h namely obtain having mobile thick base polyurethane prepolymer for use as;
3. the base polyurethane prepolymer for use as that 2. step is prepared is coated on the poriferous titanium dioxide layer that 1. step be deposited on the titanio surface, then put into hermetic container, evacuation, the negative pressure 0.5h of maintenance 0.01Mpa～0.06MPa ~ 1h, base polyurethane prepolymer for use as is penetrated in the hole of poriferous titanium dioxide layer, and forming the layer of polyurethane of one deck drawout on the surface of poriferous titanium dioxide layer, the amount of described base polyurethane prepolymer for use as is limited as the layer of polyurethane of 0.15mm～0.25mm can form thickness;
4. the surface that 3. step is obtained has the complex of layer of polyurethane to be immersed in the expanding chain pharmaceutical solution that chain extender concentration is 0.3g/ml ~ 0.8g/ml, and the inferior stannum of adding octoate catalyst, then under normal pressure, be heated to 50 ℃～55 ℃ insulation 2 h ~ 3h, after insulation finishes, described complex is taken out from expanding chain pharmaceutical solution, at room temperature in air, naturally dry, namely obtain bionic tooth implant, the amount of described expanding chain pharmaceutical solution has the compound physical ability of layer of polyurethane to flood fully with the surface to be limited, and the inferior stannum of described octoate catalyst is 0.2% ~ 0.5% of expanding chain pharmaceutical solution volume.
4. the preparation method of described bionic tooth implant according to claim 3 is characterized in that chain extender is triethanolamine or trimethylolpropane, and the solvent of chain extender is acetone or DMF.
5. according to claim 3 or the preparation method of 4 described bionic tooth implants, the particle diameter that it is characterized in that described titania powder is 50 μ m ~ 100 μ m.
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| CN201210384731.1A CN102861357B (en) | 2012-10-11 | 2012-10-11 | Bionic dental implant and preparation method thereof |
| PCT/CN2013/079112 WO2014056336A1 (en) | 2012-10-11 | 2013-07-10 | Bionic tooth implant and preparation method thereof |
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| CN201210384731.1A CN102861357B (en) | 2012-10-11 | 2012-10-11 | Bionic dental implant and preparation method thereof |
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Cited By (4)
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| WO2014056336A1 (en) * | 2012-10-11 | 2014-04-17 | 四川大学 | Bionic tooth implant and preparation method thereof |
| CN109200336A (en) * | 2018-09-11 | 2019-01-15 | 佛山市佛冠义齿有限公司 | A kind of dental implant materials and preparation method thereof |
| CN111110922A (en) * | 2019-12-25 | 2020-05-08 | 四川大学 | Periodontal biological module for 3D biological printing and construction method and application thereof |
| CN112225295A (en) * | 2020-10-19 | 2021-01-15 | 南京理工大学 | Tubular microporous titanium-based ruthenium oxide film anode applied to wastewater treatment and preparation method thereof |
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| IL238862B (en) | 2015-05-17 | 2022-02-01 | Mis Implants Tech Ltd | Dental prosthetic |
| CN111760070B (en) * | 2020-08-04 | 2022-08-05 | 北京劲松口腔医院有限公司 | Dental implant material for oral cosmetology and preparation method thereof |
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| CN112225295B (en) * | 2020-10-19 | 2021-10-15 | 南京理工大学 | Tubular microporous titanium-based ruthenium oxide film anode applied to wastewater treatment and preparation method thereof |
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| CN102861357B (en) | 2014-06-11 |
| WO2014056336A1 (en) | 2014-04-17 |
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